CN115786747A - Preparation method of medical high-performance antibacterial titanium alloy plate - Google Patents
Preparation method of medical high-performance antibacterial titanium alloy plate Download PDFInfo
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- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 123
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000005096 rolling process Methods 0.000 claims abstract description 40
- 238000000137 annealing Methods 0.000 claims abstract description 31
- 238000003723 Smelting Methods 0.000 claims abstract description 22
- 238000010275 isothermal forging Methods 0.000 claims abstract description 18
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Abstract
The invention discloses a preparation method of a medical high-performance antibacterial titanium alloy plate, which comprises the following steps: 1. smelting by using a vacuum magnetic suspension induction smelting furnace to obtain a titanium alloy ingot; 2. removing risers and defects of titanium alloy ingots, trimming and grinding the titanium alloy ingots into cylindrical ingots, annealing, and carrying out isothermal forging to obtain grain-refined slabs; 3. carrying out low-temperature annealing treatment on the grain-refined plate blank, then carrying out warm rolling, flattening and acid pickling to obtain a plate; 4. and (4) wrapping the plates, accumulating and rolling to obtain the medical high-performance antibacterial titanium alloy plate. The invention combines vacuum magnetic suspension smelting with isothermal forging with large deformation of two-phase region, so that the titanium alloy plate has equiaxial ultrafine grain structure, bright and flat surface, better biomechanical adaptation degree of product strength and elastic modulus plasticity, stable and durable antibacterial performance and excellent osseointegration characteristic.
Description
Technical Field
The invention belongs to the technical field of titanium alloy material processing, and particularly relates to a preparation method of a medical high-performance antibacterial titanium alloy plate.
Background
At present, surgical implantation medical instruments such as dental implants, artificial joints and the like are widely applied to various bone wound and bone defect patients, and the most applied medical materials are pure titanium and Ti6Al4V titanium alloy. With the development of the medical industry in recent years, a new group of low modulus titanium alloys has also been incorporated into the international standards for surgical implants, such as: ti-13Nb-13Zr, ti-13Nb-13Zr (ASTM F1713), ti-12Mo-6Zr-2Fe (ASTM F1813), ti-15Mo (ASTM F2066), ti-15Mo-5Zr-3Al (JIS T7401-6), ti-45Nb (AMS 4982), ti-2.5Al-5Mo-5V (VT 16), ti-5Al-2Sn (VT 5-1), etc., and these alloys have been widely used for the production of various medical devices such as femoral stems, artificial joints, implants, etc., because of their low elastic modulus. However, long-term clinical studies show that the strength of the instrument is low, and infection or inflammation occurs due to the fact that a bacterial biofilm is easily formed in a complex microenvironment for a long time, so that medical accidents such as operation failure and the like are rare. Therefore, in order to solve the technical problems that the existing medical titanium alloy body is easy to infect, the strength is insufficient and the like, reduce the stress shielding effect between the implant body and the self body, further improve and widen the service performance of the existing implanting apparatus, improve the technological level and the competitiveness of the titanium alloy industry and the medical apparatus industry in China, and realize the medical beta titanium alloy material and the apparatus which have multiple effects, low cost, low modulus, high strength and strong antibacterial property, the method is urgent.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of a medical high-performance antibacterial titanium alloy plate aiming at the defects of the prior art. The method combines vacuum magnetic suspension smelting with isothermal forging with large deformation of two phase regions, so that the titanium alloy plate has equiaxial ultrafine grain structure, bright and flat surface, good biomechanical adaptability of product strength and elastic modulus plasticity, stable and durable antibacterial performance and excellent osseointegration characteristic, and solves the problems of easy infection, insufficient strength and stress shielding effect of the conventional medical titanium alloy body
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a preparation method of a medical high-performance antibacterial titanium alloy plate is characterized by comprising the following steps:
step one, smelting for 2-3 times by using a vacuum magnetic suspension induction smelting furnace to obtain a titanium alloy ingot casting with uniform components;
step two, removing risers and defects of the titanium alloy ingots obtained in the step one, grinding the titanium alloy ingots into cylindrical ingots, annealing for 1-2 h at 780-850 ℃, and carrying out isothermal forging on the annealed cylindrical ingots by adopting superplastic forming equipment or thermal forming equipment, wherein the forging rate is 0.2-0.3 mm/s, the forging temperature is 650-800 ℃, and the forging deformation is 50-80%, so as to obtain grain-refined plate blanks;
step three, carrying out low-temperature annealing treatment on the grain-refined plate blank obtained in the step two, then carrying out warm rolling, and then flattening and acid washing to obtain a plate with the thickness of 1-5 mm;
step four, performing sheath covering and accumulated rolling on the plate obtained in the step three to obtain a medical high-performance antibacterial titanium alloy plate with the thickness of 0.1-1 mm; the medical high-performance antibacterial titanium alloy plate consists of the following element components in percentage by mass: 10 to 25 percent of Mo, 0.2 to 5 percent of Ag, less than or equal to 0.15 percent of impurity O and the balance of Ti.
The method comprises the steps of firstly preparing a titanium alloy cast ingot by using a vacuum magnetic suspension induction melting furnace, polishing the titanium alloy cast ingot into a cylindrical ingot, annealing to promote homogenization of alloy elements and reduce dendrite segregation, then carrying out isothermal forging, controlling the isothermal forging process to obtain an ultrafine grain structure to obtain a fine-grained plate blank, carrying out low-temperature annealing treatment to eliminate processing stress of the isothermal forging, continuously carrying out warm rolling and thinning to obtain a plate with the thickness of 1-5 mm, and then wrapping the plate and carrying out accumulated stack rolling to obtain a medical high-performance antibacterial titanium alloy plate with the thickness of 0.1-1 mm. Finally, the microstructure of the medical high-performance antibacterial titanium alloy plate prepared by the invention is an equiaxial ultrafine crystal structure, the surface is bright and flat, the strength and the elastic modulus plasticity of the product reach better biomechanical suitability, the antibacterial performance is stable and durable, and the medical high-performance antibacterial titanium alloy plate has excellent osseointegration characteristics, so that the titanium alloy has the performances of low modulus, high strength, good antibacterial performance, osseointegration capability and the like.
In the preparation process, the characteristic that electromagnetic induction stirring is adopted in vacuum magnetic suspension induction smelting is utilized, so that the smelting raw materials are not in contact with a crucible or the contact area is smaller, the stability, the cleanness and the uniformity of components of the titanium alloy ingot are improved, and the preparation method is particularly suitable for titanium alloy components consisting of low-melting-point antibacterial elements and refractory alloy elements, so that the product titanium alloy plate has low modulus, high strength, good antibacterial property and osseointegration force performance, is suitable for medical use, overcomes the problems that alloy components are unstable, the crucible is polluted and even damaged tolerance equipment are caused by serious volatilization of the low-melting-point antibacterial elements due to large difference of melting points among the elements of the alloy ingot prepared by the traditional consumable melting method, and simultaneously overcomes the problem that the strength and the toughness of the alloy ingot prepared by the powder metallurgy method are not matched due to the formation of inevitable pores.
The invention adopts an isothermal forging process for carrying out large deformation in a two-phase region after annealing, firstly utilizes high-temperature annealing to soften a titanium alloy ingot and promote the diffusion of alloy elements to tend to be uniformly distributed, removes residual stress, provides conditions for subsequent large superplastic deformation in the two-phase region, then controls the temperature, deformation rate and deformation amount of isothermal forging and pressing, and utilizes superplastic forming equipment or hot forming equipment to enable the interior of the alloy to generate higher plastic strain so as to increase necessary dislocation density, so that a local structure is turned to a high crystal boundary from a low-angle crystal boundary and forms a large amount of refined subgrains with a deformation structure, thereby obtaining a grain-refined plate blank. The process improves the strength, modulus, plasticity and toughness of the titanium alloy plate in a fine grain strengthening mode, obtains unique performance which cannot be achieved by a coarse grain structure after the structure of the titanium alloy plate reaches ultra-fine grain or nano-crystallization, and particularly greatly improves the antibacterial performance and osseointegration capability of the titanium alloy plate.
The medical high-performance antibacterial titanium alloy plate prepared by the invention is beta-type titanium alloy, the Young modulus of the titanium alloy is lower, the strength of the titanium alloy is far higher than that of Ti-Nb series, ti-Zr series and Ti-Ta series titanium alloys, and the medical high-performance antibacterial titanium alloy plate has excellent biocompatibility, high strength and high plasticity compared with the traditional medical titanium alloy and is easy to match with the elastic modulus of human bones; meanwhile, the titanium alloy effectively inhibits the atrophy of bones and promotes the reconstruction of new bones, particularly, the elastic modulus of the titanium alloy is obviously reduced after fine grain strengthening and is closer to the elastic modulus of cortical bones, so that the stress shielding caused by the fact that the elastic modulus of the titanium alloy is far greater than that of the cortical bones is reduced, the hardness of the titanium alloy is also enhanced, the generation of bone joint face abrasive dust is reduced, and favorable conditions are provided for the adhesion, differentiation and proliferation of cells in vivo. In addition, the titanium alloy has more particle boundaries, so that a large number of free electrons are obtained, higher activation energy is provided, calcium and phosphorus deposition on the surface of the titanium alloy is promoted, and in-vivo osseointegration is further promoted.
The preparation method of the medical high-performance antibacterial titanium alloy plate is characterized in that in the third step, the low-temperature annealing treatment is carried out at the temperature of 400-500 ℃, and the heat preservation time is 30-60 min; the pass deformation of warm rolling is 15-25%. The structure of the grain-refined slab obtained by isothermal forging has high energy storage, so that the grain-refined slab is in a metastable state or an unbalanced structural state, the ductility and the thermal stability of the material can be reduced, and the practical application of the material is seriously limited.
The preparation method of the medical high-performance antibacterial titanium alloy plate is characterized in that in the fourth step, the sheath is made of a 304L stainless steel plate with the thickness of 1-2 mm, and the total accumulated and rolled deformation is more than 80%. According to the invention, the 304L stainless steel plate which is highly matched with the plasticity of the titanium alloy and even superior to the plasticity of the titanium alloy is selected as the sheathing material, and the thickness of the sheathing material is controlled in a combined manner, so that the uniform consistency of the plastic deformation of the plate and the sheathing material in the subsequent accumulative rolling deformation process is facilitated, the surface quality of the plate is improved, the dimensional precision is improved, the anisotropy of the plate is reduced, and the conditions that the sheathing material generates a large amount of plastic deformation before the plate due to too large thickness of the sheathing material and the excessive thinning due to too small thickness of the sheathing material are avoided. The invention controls the total deformation of the accumulated rolling to be more than 80 percent, so that the plate obtains larger accumulated deformation, the structure of the plate is effectively refined, the strength of the plate is improved, and uneven grain deformation or rotation caused by insufficient deformation is avoided.
The preparation method of the medical high-performance antibacterial titanium alloy plate is characterized in that the tensile strength of the medical high-performance antibacterial titanium alloy plate in the fourth step is 937 MPa-1308 MPa, the yield strength is 919 MPa-1242 MPa, the elastic modulus is 72 GPa-76 GPa, the elongation is 15.5% -21%, and the microhardness HV is 360-430.
Compared with the prior art, the invention has the following advantages:
1. the invention carries out coping, annealing, isothermal forging, low-temperature flaming treatment, warm rolling, wrapping and accumulated rolling on the titanium alloy ingot prepared by vacuum magnetic suspension induction melting in sequence to obtain the medical high-performance antibacterial titanium alloy plate.
2. The medical high-performance antibacterial titanium alloy plate prepared by the invention has the performances of low modulus, high strength, good antibacterial property, osseointegration capability and the like, and the thickness is 0.1-1 mm, thereby meeting the requirements of titanium alloy implantation medical instruments.
3. The preparation method has the advantages of simple process, low cost, reusable residual materials and low requirement on equipment, can realize the preparation of the high-performance antibacterial titanium alloy plate by adopting a common hydraulic press and a rolling mill, meets the production requirement of small-batch finished products, has strong repeatability, and is suitable for industrial production.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
Fig. 1 is a TEM microscopic morphology of the medical high-performance antibacterial titanium alloy plate prepared in example 1 of the present invention.
Fig. 2 is a room temperature tensile property curve diagram of the medical high-performance antibacterial titanium alloy sheet prepared in examples 1 to 6 of the present invention.
FIG. 3 is a bar graph of cell viability values of medical high-performance antibacterial titanium alloy sheets prepared in examples 1 to 2 and 4 and 6 of the present invention after culturing for 1, 3 and 5 days with comparative samples.
Detailed Description
Example 1
The embodiment comprises the following steps:
step one, smelting for 2 times by using a vacuum magnetic suspension induction smelting furnace to obtain a titanium alloy ingot with uniform components;
step two, removing risers and defects of the titanium alloy ingot obtained in the step one, grinding the titanium alloy ingot into a cylindrical ingot, annealing the cylindrical ingot at 780 ℃ for 1h, and carrying out isothermal forging on the annealed cylindrical ingot by adopting 1250 hot forming equipment, wherein the forging rate is 0.2mm/s, the forging temperature is 650 ℃, and the forging deformation is 50%, so as to obtain a grain-refined plate blank;
step three, carrying out low-temperature annealing treatment on the grain-refined plate blank obtained in the step two, then carrying out warm rolling, and then carrying out leveling and acid pickling to obtain a plate with the thickness of 1 mm; the temperature of the low-temperature annealing treatment is 400 ℃, and the heat preservation time is 60min; the pass deformation of warm rolling is 15%;
step four, sheathing and accumulating and rolling the plate obtained in the step three to obtain a medical high-performance antibacterial titanium alloy plate with the thickness of 0.1 mm; the medical high-performance antibacterial titanium alloy plate consists of the following element components in percentage by mass: 10% of Mo, 0.2% of Ag, 0.06% of impurity O and the balance of Ti; the sheath is made of a 304L stainless steel plate with the thickness of 1mm, and the total accumulated pack rolling deformation is 90%.
Fig. 1 is a TEM microscopic morphology of the medical high-performance antibacterial titanium alloy plate prepared in this embodiment, and as can be seen from fig. 1, the medical high-performance antibacterial titanium alloy plate has a uniform ultrafine grain structure, an average grain size of about 200nm, and a phase structure of β phase.
Example 2
The embodiment comprises the following steps:
step one, smelting for 2 times by using a vacuum magnetic suspension induction smelting furnace to obtain a titanium alloy ingot with uniform components;
step two, removing risers and defects of the titanium alloy ingot obtained in the step one, grinding the titanium alloy ingot into a cylindrical ingot, annealing the cylindrical ingot at 780 ℃ for 1.5 hours, and carrying out isothermal forging on the annealed cylindrical ingot by adopting 680 thermal forming equipment, wherein the forging rate is 0.2mm/s, the forging temperature is 700 ℃, and the forging deformation is 60%, so as to obtain a grain-refined plate blank;
step three, carrying out low-temperature annealing treatment on the grain-refined plate blank obtained in the step two, then carrying out warm rolling, and then carrying out leveling and acid pickling to obtain a plate with the thickness of 2 mm; the temperature of the low-temperature annealing treatment is 420 ℃, and the heat preservation time is 60min; the pass deformation of warm rolling is 20%;
step four, performing sheath covering and accumulated rolling on the plate obtained in the step three to obtain a medical high-performance antibacterial titanium alloy plate with the thickness of 0.2 mm; the medical high-performance antibacterial titanium alloy plate consists of the following element components in percentage by mass: 15% of Mo, 1% of Ag, 0.09% of impurity O and the balance of Ti; the sheath is made of a 304L stainless steel plate with the thickness of 1.5mm, and the total accumulated pack rolling deformation is 90%.
Example 3
The embodiment comprises the following steps:
step one, smelting for 2 times by using a vacuum magnetic suspension induction smelting furnace to obtain a titanium alloy ingot with uniform components;
step two, removing a dead head and polishing defects of the titanium alloy ingot obtained in the step one to form a cylindrical ingot, annealing at 800 ℃ for 1.5 hours, and carrying out isothermal forging on the annealed cylindrical ingot by adopting 630T superplastic forming equipment, wherein the forging rate is 0.2mm/s, the forging temperature is 700 ℃, and the forging deformation is 60%, so as to obtain a grain-refined plate blank;
step three, carrying out low-temperature annealing treatment on the grain-refined plate blank obtained in the step two, then carrying out warm rolling, and then flattening and acid washing to obtain a plate with the thickness of 3 mm; the temperature of the low-temperature annealing treatment is 450 ℃, and the heat preservation time is 50min; the pass deformation of warm rolling is 20%;
step four, performing sheath covering and accumulated rolling on the plate obtained in the step three to obtain a medical high-performance antibacterial titanium alloy plate with the thickness of 0.4 mm; the medical high-performance antibacterial titanium alloy plate consists of the following element components in percentage by mass: 10% of Mo, 3% of Ag, 0.09% of impurity O and the balance of Ti; the sheath is made of a 304L stainless steel plate with the thickness of 1.5mm, and the total accumulated pack rolling deformation is 86.7%.
Example 4
The embodiment comprises the following steps:
step one, smelting for 3 times by using a vacuum magnetic suspension induction smelting furnace to obtain a titanium alloy ingot with uniform components;
step two, removing risers and defects of the titanium alloy ingot obtained in the step one, grinding the titanium alloy ingot into a cylindrical ingot, annealing the cylindrical ingot at 820 ℃ for 1.5 hours, and carrying out isothermal forging on the annealed cylindrical ingot by adopting 1250 hot forming equipment, wherein the forging rate is 0.23mm/s, the forging temperature is 730 ℃, and the forging deformation is 65%, so as to obtain a grain-refined plate blank;
step three, carrying out low-temperature annealing treatment on the grain-refined plate blank obtained in the step two, then carrying out warm rolling, and then carrying out leveling and acid pickling to obtain a plate with the thickness of 3.5 mm; the temperature of the low-temperature annealing treatment is 470 ℃, and the heat preservation time is 40min; the pass deformation of warm rolling is 22%;
step four, sheathing and accumulating and rolling the plate obtained in the step three to obtain a medical high-performance antibacterial titanium alloy plate with the thickness of 0.5 mm; the medical high-performance antibacterial titanium alloy plate consists of the following element components in percentage by mass: 10% of Mo, 3% of Ag, 0.1% of impurity O and the balance of Ti; the sheath is made of a 304L stainless steel plate with the thickness of 2mm, and the total accumulated pack rolling deformation is 85.7%.
Example 5
The embodiment comprises the following steps:
step one, smelting for 3 times by using a vacuum magnetic suspension induction smelting furnace to obtain a titanium alloy ingot with uniform components;
step two, removing risers and defects of the titanium alloy ingots obtained in the step one, grinding the titanium alloy ingots into cylindrical ingots, annealing for 1.5 hours at 850 ℃, and carrying out isothermal forging on the annealed cylindrical ingots by adopting 680 thermal forming equipment, wherein the forging rate is 0.25mm/s, the forging temperature is 750 ℃, and the forging deformation is 70%, so as to obtain grain-refined slabs;
step three, carrying out low-temperature annealing treatment on the grain-refined plate blank obtained in the step two, then carrying out warm rolling, and then flattening and acid washing to obtain a plate with the thickness of 4 mm; the temperature of the low-temperature annealing treatment is 480 ℃, and the heat preservation time is 40min; the pass deformation of warm rolling is 25%;
step four, performing sheath covering and accumulated rolling on the plate obtained in the step three to obtain a medical high-performance antibacterial titanium alloy plate with the thickness of 0.8 mm; the medical high-performance antibacterial titanium alloy plate consists of the following element components in percentage by mass: 15% of Mo, 3.3% of Ag, 0.12% of impurity O and the balance of Ti; the sheath is made of a 304L stainless steel plate with the thickness of 2mm, and the total accumulated pack rolling deformation is 80%.
Example 6
The embodiment comprises the following steps:
step one, smelting for 3 times by using a vacuum magnetic suspension induction smelting furnace to obtain a titanium alloy ingot with uniform components;
step two, removing risers and defects of the titanium alloy ingot obtained in the step one, grinding the titanium alloy ingot into a cylindrical ingot, annealing the cylindrical ingot at 850 ℃ for 2 hours, and carrying out isothermal forging on the annealed cylindrical ingot by adopting 630T superplastic forming equipment, wherein the forging rate is 0.3mm/s, the forging temperature is 800 ℃, and the forging deformation is 80%, so as to obtain a grain-refined plate blank;
step three, carrying out low-temperature annealing treatment on the grain-refined plate blank obtained in the step two, then carrying out warm rolling, and then carrying out leveling and acid pickling to obtain a plate with the thickness of 5 mm; the temperature of the low-temperature annealing treatment is 500 ℃, and the heat preservation time is 30min; the pass deformation of warm rolling is 20%;
step four, performing sheath covering and accumulated rolling on the plate obtained in the step three to obtain a medical high-performance antibacterial titanium alloy plate with the thickness of 1 mm; the medical high-performance antibacterial titanium alloy plate consists of the following element components in percentage by mass: 25% of Mo, 5% of Ag, 0.15% of impurity O and the balance of Ti; the sheath is made of a 304L stainless steel plate with the thickness of 1.5mm, and the total accumulated pack rolling deformation is 80%.
According to GB/T13810-2017 titanium and titanium alloy for surgical implants and GB/T228-2002 tensile test samples of room temperature plates, the room temperature performance of the medical high-performance antibacterial titanium alloy plates prepared in the embodiments 1-6 is tested, and the results are shown in the table 1 and the figure 2.
Table 1 properties of medical high-performance antibacterial titanium alloy sheet prepared in examples 1 to 6 of the present invention
As can be seen from Table 1, the medical high-performance antibacterial titanium alloy plates prepared in the embodiments 1 to 6 have the average grain size of 0.2 to 0.8 μm, the tensile strength of 937 to 1308MPa, the yield strength of 919 to 1242MPa, the elastic modulus of 72 to 76GPa, the elongation of 15.5 to 21 percent, the microhardness HV of 360 to 430 and the antibacterial rate of more than 94 percent, which indicates that the medical high-performance antibacterial titanium alloy plates prepared by the invention have the advantages of low modulus, high strength, good antibacterial property and bone integration capability. Compared with the common medical Ti-15Mo plate with the same thickness, the medical high-performance antibacterial titanium alloy plate prepared in the embodiment 6 has smaller average grain size, and the superfine grain of the microstructure is realized, so that the tensile strength, the yield strength, the elastic modulus, the elongation, the microhardness HV and the antibacterial rate of the medical high-performance antibacterial titanium alloy plate are all superior to those of the common medical Ti-15Mo plate.
Fig. 2 is a room temperature tensile property curve diagram of the medical high-performance antibacterial titanium alloy plates prepared in examples 1 to 6 of the present invention, and it can be seen from fig. 2 that the medical high-performance antibacterial titanium alloy plates prepared in the present invention have tensile strength of more than 930MPa and elongation after fracture of more than 15.5% while maintaining low elastic modulus (72 GPa to 76 GPa), which indicates that the medical high-performance antibacterial titanium alloy plates have high adaptability to biomechanical properties, and are a novel high-performance antibacterial beta titanium alloy very suitable for surgical implantation.
The medical high-performance antibacterial titanium alloy plates prepared in the embodiments 1 to 2, 4 and 6 of the invention and a comparison sample are subjected to cell culture and cell viability value detection, an osteoblast system (MC 3T 3-E1) is selected as a model for evaluating cell biocompatibility, a conventional medical Ti-15Mo titanium alloy is selected as a comparison sample, and cell attachment and proliferation are analyzed by a commercial Live-Dead staining kit and an AlamarBlue assay kit (Life Technologies), wherein the specific process is as follows: first, prior to cell culture, samples of comparative example and each example were sterilized with 75% ethanol for 2h and irradiated with Ultraviolet (UV) for 30min, and then placed in 24-well culture plates, and cells were seeded on the surface of each sample at a density of 4000 cells/cm 2 Adding an indicator of an AlamarBlue assay kit into each well after 1 day, 3 days and 5 days of inoculation culture, incubating for 4 hours, adding 100 mu L of culture medium into a 96-well black plate, recording fluorescence intensity by using a microplate reader (Spectramax i3, molecular Devices), and testing at least 3 samples; finally, live cells and Dead cells were stained conventionally by Live-Dead kit assay, and the adhesion state of the stained cells on the surface of each titanium alloy plate was observed by an upright fluorescence microscope (BX 53, olympus), and the cell viability value of each titanium alloy plate was calculated and plotted in a bar graph, with the results shown in fig. 3.
Fig. 3 is a bar graph of cell viability values of the medical high-performance antibacterial titanium alloy plates prepared in examples 1 to 2, 4 and 6 of the present invention after culturing for 1, 3 and 5 days with the comparative samples, and it can be seen from fig. 3 that the surfaces of the medical high-performance antibacterial titanium alloy plates of the comparative samples and the examples have significantly different cell proliferation capacities under the same culture time and conditions, i.e., the medical high-performance antibacterial titanium alloy plates prepared in the present invention have a larger cell viability value and a better differentiation and proliferation capacity compared with the conventional Ti-15Mo medical titanium alloy; meanwhile, the cell proliferation rate is also obviously increased along with the increase of the culture days, particularly, the average grain size of equiaxed ultrafine grains in the titanium alloy plate is closer to the nanometer level, the cell proliferation capacity is stronger, but when the average grain size is more than 200nm, the cell proliferation capacity is not obviously different.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modifications, alterations and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (4)
1. A preparation method of a medical high-performance antibacterial titanium alloy plate is characterized by comprising the following steps:
step one, smelting for 2-3 times by using a vacuum magnetic suspension induction smelting furnace to obtain a titanium alloy ingot with uniform components;
step two, removing risers and defects of the titanium alloy ingots obtained in the step one, grinding the titanium alloy ingots into cylindrical ingots, annealing for 1-2 h at 780-850 ℃, and carrying out isothermal forging on the annealed cylindrical ingots by adopting superplastic forming equipment or thermal forming equipment, wherein the forging rate is 0.2-0.3 mm/s, the forging temperature is 650-800 ℃, and the forging deformation is 50-80%, so as to obtain grain-refined plate blanks;
step three, carrying out low-temperature annealing treatment on the grain-refined plate blank obtained in the step two, then carrying out warm rolling, and then carrying out leveling and acid pickling to obtain a plate with the thickness of 1-5 mm;
step four, sheathing and accumulating and rolling the plate obtained in the step three to obtain a medical high-performance antibacterial titanium alloy plate with the thickness of 0.1-1 mm; the medical high-performance antibacterial titanium alloy plate consists of the following element components in percentage by mass: 10 to 25 percent of Mo, 0.2 to 5 percent of Ag, less than or equal to 0.15 percent of impurity O and the balance of Ti.
2. The preparation method of the medical high-performance antibacterial titanium alloy sheet material according to claim 1, wherein the temperature of the low-temperature annealing treatment in the step three is 400-500 ℃, and the heat preservation time is 30-60 min; the pass deformation of warm rolling is 15-25%.
3. The method for preparing the medical high-performance antibacterial titanium alloy plate according to claim 1, wherein the sheath in the fourth step is made of a 304L stainless steel plate with the thickness of 1 mm-2 mm, and the total accumulated pack rolling deformation is more than 80%.
4. The method for preparing the medical high-performance antibacterial titanium alloy plate according to claim 1, wherein the medical high-performance antibacterial titanium alloy plate in the fourth step has tensile strength of 937MPa to 1308MPa, yield strength of 919MPa to 1242MPa, elastic modulus of 72GPa to 76GPa, elongation of 15.5 percent to 21 percent and microhardness HV of 360 to 430.
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| CN117400603A (en) * | 2023-12-13 | 2024-01-16 | 内蒙金属材料研究所 | High-speed impact resistant laminated titanium alloy plate and preparation method thereof |
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